Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0075—Antistatics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

• This disclosure generally relates to compositions comprising at least one polymer and at least one antistatic agent and more particularly, relates to fibers, films, fabrics, coatings, and molded or blown articles comprising the antistatic polymer compositions. In other aspects, this disclosure also relates to processes for imparting antistatic characteristics to substrates.
• Static electricity is generated whenever dissimilar materials move or abrade against another object. In the case of immobile objects, even friction on the surface with ambient air can create static electricity.
• the charge capacity of a substance defined as the capacity to generate static electricity, depends on, among others, the condition of its surface, the dielectric constant, the surface resistivity, and the relative humidity. Because charge capacity is directly proportional to the surface resistivity, it follows that a material with higher surface resistivity, or one that is better insulator will tend to generate a greater static charge. Accumulated static charge on an insulating surface can range from a few volts up to several hundred thousand volts. Thus, electrostatic discharge becomes an increasingly worrying issue at higher levels of static charge buildup. High levels of static electricity can cause permanent damage to electronic components that work typically at microvolt levels.
• polymers that are used to make plastics are extremely good insulators, or in other words, they have an extremely low surface conductance, or an extremely high surface resistivity. This property makes polymers useful for fabricating electrical equipment.
• polymers can build large electrical charges that create dirt-attracting forces and naturally seek a conductive discharge path.
• polymers generally have very low surface conductance, thus, the decay or discharge rate lasts a very long time, a time during which the material would retain the charge, and thus attract and retain dirt particles.
• Antistatic agents constitute a unique class of polymer additives and provide a measure of safety by preventing any fire, resulting from sparking, caused by an accumulation of static electricity on the surface of an article fabricated of the polymer. They also offer aesthetic values by preventing the accumulation of surface dust on the article.
• lenses of automotive headlamps are typically made of polymers, such as polycarbonates, which have the desirable combination of heat stability, dimensional stability, transparency, and ductility.
• the optics system also sometimes called “Fresnel” necessary to properly focus the headlight beam on the road did not have a smooth profile. Consequently, the dust that accumulated on the lens surface, either during the lens molding step, or during the service life of the headlamp, was not conspicuously visible.
• conveyor belt design Another important area, where mitigation of static charge buildup is critical, is in conveyor belt design.
• metal conveyor belts have been replaced and are made mostly of plastics and/or synthetic polymeric materials.
• the replacement of metal with plastic has led to several distinct advantages in conveyor belt technology, such as cleanliness (plastic parts shed fewer particles), reliability (plastic conveyor belts work for very long hours without attention), relatively lower noise (plastic parts naturally damp out clanging and resonant vibration that typically accompany metal based processes), low cost to lifetime ratio (plastic parts undergo much slower mechanical abrasion than metal-based systems), modularity and flexibility, precision due to tight tolerances in the original plastic conveyor components, and automation adaptability made possible by simple retrofit of external systems under electric control.
• plastics-based conveyor systems began to be used in hyper-clean environments (Class 100 or higher) essential for manufacture of advanced electronics products and systems.
• electrostatic discharge a phenomenon inherent in plastic materials formulated without antistatic agents, posed difficulties to the high technology manufacturer employing plastic conveyor belt components.
• the buildup of surface charge also results in secondary dirt contamination, which has undesirable consequences, especially for precision, high technology electronic components.
• the conveyor belt functions through a combination of motion and friction, the belts tend to build up large amounts of electrostatic charge on their surface, thus leading to an increased possibility of electrostatic discharge.
• the damaging consequences of an electrostatic charge on precision electronic equipments have already been described above. It therefore becomes clear that for synthetic polymers to continue to serve the increasingly demanding requirements of the conveyor belt market, more effective plastic materials capable of effective surface charge dissipation are required.
• Antistatic agents have generally been applied in one of two ways: externally and internally. Spraying the surface, or dipping the polymeric plastic material in a medium containing the antistatic agent can be used to externally apply the antistatic agents. On the other hand, internally applied antistatic agents are generally added to the polymer before processing. For this reason, internal antistatic agents have to be thermally stable and be able to migrate to the surface during processing to impart the most effective antistatic decay behavior.
• antistatic agents having a surface-active component (surfactant-like) within its structure.
• Internal antistatic agents of the anionic surfactant type are generally difficult to handle because they are inferior in compatibility and uniform dispersibility.
• Cationic surfactants containing quaternary nitrogen have good antistatic characteristics, but have limited utility.
• Non-ionic surfactants generally have inferior antistatic characteristics compared to the ionic varieties.
• due to the limited thermal stability of surfactants in general they are typically not used for processing engineering thermoplastics, such as polycarbonates.
• Metal salts of organic sulfonic acids have been used as antistatic agents, but they are not thermally stable, and not sufficiently compatible with resins.
• antistatic additives and compositions thereof described herein are extremely useful for producing articles with outstanding abilities to dissipate static charge buildup, and mitigate or eliminate problems due to dust attraction/repulsion. This in turn leads to enhanced performance, safety, and aesthetic features for these articles.
• one embodiment of the disclosure is a quaternary onium aromatic sulfonate having the formula: wherein each R 1 independently comprises aliphatic or aromatic, substituted or unsubstituted, carbocyclic or heterocyclic radicals, each X is selected from the group consisting of phosphorus and nitrogen; “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; E comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein R is a monovalent hydrocarbon group; “q” represents any integer from and including zero through the number of positions on G 1 available for substitution; “t
• an antistatic composition comprises a melt blend of an aromatic sulfonate compound and a thermoplastic polymer, wherein the aromatic sulfonate compound is represented by the formula: wherein each R 1 independently comprises aliphatic or aromatic, substituted or unsubstituted, carbocyclic or heterocyclic radicals, each “X” is selected from the group consisting of phosphorus and nitrogen; “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; E comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein “R” is a monovalent hydrocarbon group; “
• a method of making a quaternary onium aromatic sulfonate compound comprises preparing in a solvent a first solution comprising an aromatic sulfonic acid salt having the formula: wherein “T” is an alkali metal, “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; “E” is an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, halogen, and OR, wherein “R” is a monovalent hydrocarbon group; “s”, “t”, and “u” each represents an integer equal to one, “X” is phosphorus and “q” represents any integer from and including zero through the number of positions on G 1 available for substitution; contacting the first solution with an acidic medium to convert the alkali metal aromatic sulfonic acid salt to an aromatic sulfonic acid; mixing the aromatic sulfonic acid with a quaternary compound; extracting the
• a method of making a quaternary onium aromatic sulfonate comprises preparing in a solvent a first solution comprising an aromatic sulfonic acid salt having the formula: wherein “T” is an alkali metal, “a” is 1 or 2, and “b” is 0; G 1 is an aromatic group; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, halogen, and “OR”, “R” is a monovalent hydrocarbon group; “s” and “u” each represents an integer equal to zero, “q” represents any integer from and including zero through the number of positions on G 1 available for substitution, “t” represents an integer equal to one; contacting the first solution with an acidic medium to convert the alkali metal aromatic sulfonic acid salt to an aromatic sulfonic acid; mixing the aromatic sulfonic acid with a quaternary compound; extracting the mixture with an organic solvent to provide a second solution; and evaporating the organic solvent from the second solution to obtain the quaternary on
• a method of making a polyorganosiloxane-functionalized aromatic sulfonate comprises forming a reaction mixture comprising a hydroxyalkyl- or a hydroxyaryl-terminated polydimethylsiloxane represented by the formula: wherein “Z” is selected from the group consisting of (CH 2 ) m′ , wherein “m′” has a value from about 2 to about 10, and divalent substituted and unsubstituted aromatic radicals; and “n′” has a value of about 5 to about 20; a quaternary sulfonate salt of an aromatic sulfocarboxylic acid having the formula: wherein each R 1 is independently selected from aliphatic or aromatic, substituted or unsubstituted, carbocyclic or heterocyclic radicals, and “X” is selected from the group consisting of phosphorus and nitrogen; a catalyst composition, and a solvent; stirring the reaction mixture; and heating the reaction mixture to a temperature and time effective to produce
• a method of making a benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate compound comprises contacting an aqueous solution of an alkali metal salt of a benzene-1-methoxy-3-n-pentadecyl-4,6-disulfonic acid with a strongly acidic type ion exchange resin to generate a free acid of the alkali metal salt in the aqueous solution; contacting the aqueous solution with tetra-n-butylphosphonium hydroxide in an amount effective to adjust a pH of the solution to about 5 to about 6; mixing the aqueous solution with an organic solvent; separating the organic solvent from the aqueous solution; and evaporating the organic solvent to obtain the benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate compound.
• a method of making a bis(tetrabutylphosphonium) polyorganosiloxane-functionalized aromatic sulfonate compound having the formula: wherein “n′′” is an integer having a value of about 7 comprises forming a reaction mixture comprising a hydroxyalkyl-terminated polydimethylsiloxane having the formula: wherein “n′′” is an integer with a value of about 7; a quaternary sulfonate salt of an aromatic sulfocarboxylic acid having the formula, a catalyst composition comprising 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, and triethylamine; a solvent; and heating the reaction mixture to a temperature and for a time effective to produce the bis(tetrabutylphosphonium) polyorganosiloxane-functionalized aromatic sulfonate compound.
• a method of making an antistatic or antidust thermoplastic polymer molding composition comprises combining an aromatic sulfonate compound with a thermoplastic resin melt processing equipment, wherein the aromatic sulfonate compound is represented by the formula: wherein each R 1 independently comprises aliphatic or aromatic, substituted or unsubstituted, carbocyclic or heterocyclic radicals, each X is selected from the group consisting of phosphorus and nitrogen; “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; E comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein R is a mono
• a method of making an antistatic or antidust thermoplastic polymer molding composition comprises combining an aromatic sulfonate compound with a thermoplastic resin melt processing equipment, wherein the aromatic sulfonate compound is represented by the formula: wherein each R 1 independently comprises aliphatic or aromatic, substituted or unsubstituted, carbocyclic or heterocyclic radicals, each X is selected from the group consisting of phosphorus and nitrogen; “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; E comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR,
• the embodiments of the present disclosure have many advantages, including the ability to produce the antistatic compounds described above, polymer molding compositions containing these compounds, and fabrication of antistatic articles useful in automotive, electronics, conveyor belt systems, and display devices applications.
• the antistatic agents are quaternary onium aromatic sulfonate salts represented by formula (I): wherein each R 1 independently preferably comprises substituted and unsubstituted, aliphatic, aromatic, hydrocarbyl, carbocyclic, or heterocyclic radicals; each “X” is selected from the group consisting of phosphorus and nitrogen; “a” is 0, 1 or 2, and “b” is 0, 1 or 2 with the proviso that (a+b) is an integer greater than or equal to 1; G 1 is an aromatic group; “E” comprises a bis(carbonyloxyalkyl) polydiorganosiloxane, a bis(carbonyloxyaryl) polydiorganosiloxane, and an ether linkage; each Y 1 independently comprises hydrogen, a monovalent hydrocarbon group, alkenyl, allyl, halogen, bromine, chlorine; nitro; and OR, wherein “
• “E” represents a polydiorganosiloxane of the formula (II): wherein “n 1 ” has a value from about 5 to about 20; and R 3 is independently selected from C 1 -C 6 linear and branched alkyl groups. In a preferred embodiment, R 3 is a methyl group.
• R 1 groups in the quaternary onium aromatic sulfonate compounds shown in formula (I) can assume a wide variation in their structures.
• Each R 1 can be the same or various combinations of the aliphatic, aromatic, hydrocarbyl, carbocyclic, and heterocyclic radicals.
• Suitable examples of R include, but are not limited to, C 1 -C 18 linear and branched alkyl radicals, aralkyl, and cycloalkyl radicals.
• R 1 is one selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-hexadecyl, and n-octadecyl.
• R 1 is an n-butyl radical.
• suitable R 1 radicals include, but are not limited to, C 6 -C 14 aromatic substituted and unsubstituted aromatic radicals.
• R 1 is preferably an unsubstituted aromatic radical selected from the group consisting of phenyl, indenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, and fluorenyl.
• R 1 is preferably a C 6 -C 14 substituted aromatic radical, which may or may not contain other heteroatom substituents.
• R 1 substituents may also comprise mixtures of alkyl, cycloalkyl, aralkyl, and aromatic groups.
• Suitable examples of the [(R 1 ) 4 X + ] fragment of the quaternary onium aromatic sulfonate compound include, but are not limited to, tetramethylammonium, tetramethylphosphonium, tetraethylammonium, tetraethylphosphonium, tetra-n-butylammonium, tetra-n-butylphosphonium, tetra-n-pentylammonium, tetra-n-pentylphosphonium, tetra-n-hexylammonium, tetra-n-hexylphosphonium, tetra-n-heptylammonium, tetra-n-heptylphosphonium, tetra-n-octylammonium, tetra-n-octylphosphonium, tetraphenylammonium, tetraphenylphosphon
• the R 1 groups preferably do not hinder formation of the quaternary onium aromatic sulfonate compound.
• the R 1 groups generally comprise 1 to 18 carbons that may further include heteroatoms such as an oxygen atom, nitrogen atom, sulfur atoms, or the like.
• heteroatoms such as an oxygen atom, nitrogen atom, sulfur atoms, or the like.
• organic groups containing oxygen atoms are hydrocarbon groups substituted with hydroxyl or alkoxy group.
• the heteroatom containing group includes, but is not limited to, hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl; and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, n-butoxyethyl, iso-butoxyethyl, polyalkylene glycol, and the like, including mixtures thereof.
• hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl
• alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, ethoxyethyl,
• heterocyclic groups for the R 1 group include, but are not limited to, substituted and unsubstituted pyridinium, pyridazinium, pyrimidinium, imidazolium, pyrazolium, pyrazinium, thiazolium, and oxazolium radicals.
• the substituted heterocyclic radicals may optionally have substituents selected from the group consisting of halogens (such as fluorine and/or chlorine), monovalent C 1 -C 6 linear and branched alkyl, monovalent C 1 -C 6 linear and branched alkoxy, and monovalent C 6 -C 12 aryloxy radicals, and mixtures thereof.
• suitable R 1 groups are those obtained by different combinations of the aliphatic, aromatic, and the heteroatom containing groups described hereinabove.
• Other examples for the [(R 1 ) 4 X + ] moiety obtained by other combinations of different types of R 1 groups in different ways, as alluded to above, will be apparent to those skilled in the art.
• the quaternary onium aromatic sulfonate preferably has a structure in which each R 1 is an n-butyl radical, X is nitrogen, “a” is 1 or 2 and “b” is zero; “s” and “u” each represents an integer equal to zero, “t” represents an integer equal to one; G 1 is a tetravalent phenyl radical, and “q” represents an integer equal to two such that Y 1 is a methoxy and an n-pentadecyl group.
• the quaternary onium aromatic sulfonate preferably has a structure in which each R 1 is an n-butyl radical, X is phosphorus, “a” is 1 or 2 and “b” is zero; “s” and “u” each represents an integer equal to zero, “t” represents an integer equal to one; G 1 is a tetravalent phenyl radical, and “q” represents an integer equal to two such that Y 1 is a methoxy and an n-pentadecyl group.
• the quaternary onium aromatic sulfonate has a structure in which each R 1 is an n-butyl radical, “a” and “b” each is 1, X is phosphorus, “s”, “t” and “u” each represents an integer each being equal to one; G 1 is a divalent aromatic radical, “q” represents an integer equal to zero, and “E” is a bis(carbonyloxyalkyl) polydiorganosiloxane linkage of the formula (III): wherein “m” has a value in the range from about 3 to about 6, and “n′” has a value in the range from about 5 to about 20.
• the quaternary onium aromatic sulfonate has the structure in which each R 1 is an n-butyl radical, “a” and “b” each is 1, X is nitrogen, “s” represents an integer equal to one, “t” and “u” represent integers each being equal to one, G 1 is a divalent aromatic radical, “q” represents an integer equal to zero, and “E” is the bis(carbonyloxyalkyl)polydiorganosiloxane linkage of formula (III).
• the quaternary onium aromatic sulfonate preferably has a structure in which each R 1 is an n-butyl radical, “E” is an ether linkage, “X” is phosphorus, “a” is 0 or 1 and “b” is one with the proviso that (a+b) is 1 or 2; R 1 is an n-butyl radical, “s”, “t”, and “u” each represents an integer equal to one; G 1 is a tri- or tetra-substituted phenyl radical, “q” represents an integer equal to one such that Y 1 is an alkyl group selected from the group consisting of C 1 to C 20 linear and branched alkyl groups.
• the quaternary onium aromatic sulfonates described hereinabove have antistatic characteristics that make them valuable as additives for preparing antistatic polymer compositions.
• antistatic is also meant to include the term “antidust” since an antistatic additive, a polymer composition or an article comprising the antistatic additive would also show the ability to repel surface dust.
• thermoset and thermoplastic polymers can be used for making polymer compositions comprising the quaternary onium aromatic sulfonate.
• the thermoplastic polymer is preferably selected from the group consisting of condensation and addition polymers.
• the thermoplastic polymer is an aromatic polycarbonate, a polyestercarbonate, a polyphenylene sulfide, a polyetherimide, a polyester, a polyphenylene ether, a polyphenylene ether/styrene polymer blends, a polyamide, a polyketone, acrylonitrile-butadiene-styrene copolymer, a styrene-acrylonitrile copolymer, a polyolefin, blends thereof, and blends thereof with other materials.
• Suitable other materials include, but are not intended to be limited to, antioxidants, thermal stabilizers, ultraviolet stabilizers, processing agents, mold release agents, fillers, flame retardants, and like additives.
• the polycarbonates and polyestercarbonates are preferably obtained from polymerization processes that include melt transesterification method, interfacial polymerization method, solid-state polymerization, solution, or redistribution processes, or combinations thereof.
• a thermoplastic polymer composition comprises an antistatic additive selected from the group of quaternary onium aromatic sulfonates as shown in formulas (IV), (V), and (VI).
• the substituent “R 2 ” (formula V) preferably occupies an ortho or a para position on the aromatic ring, and is independently selected from the group consisting of C 1 to C 20 linear and branched alkyl groups.
• the term “a′” (formula IV) preferably has a value of about zero or one.
• n′′ (formula VI) has a value of about 7.
• thermoplastic polymer compositions preferably comprise the additive at about 2.5 ⁇ 10 ⁇ 3 parts to about 6 parts per 100 parts of the total amount of polymer in the composition, with about 3 ⁇ 10 ⁇ 2 parts to about 6 parts per 100 parts more preferred, and with about 0.5 parts to about 6 parts per 100 parts even more preferred.
• a method for preparing the quaternary onium aromatic sulfonate salts of formula (I) comprises the use of aromatic sulfonic acid salts generally represented by formula (VII): wherein “a”, “b”, “t”, “s”, “u” G 1 , Y 1 , and “q” are the same described earlier for formula (I); “T” is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
• an acidic medium is used to generate the corresponding sulfonic acid.
• suitable acidic mediums include strong acids such as for example sulfuric acid, fluoroalkylsulfonic acids and perfluoroalkylsulfonic acids.
• the acidic medium comprises a polymeric, strongly acidic ion exchange resin bearing sulfonic acid groups.
• polymeric, strongly acidic ion exchange resin bearing sulfonic acid groups include, but are not limited to fluorinated polymeric sulfonic acid resins, such as the Nafion® series of resins (available commercially from E. I.
• the sulfonated styrene-divinylbenzene copolymers comprise gelular and macroreticular varieties, corresponding to the sulfonated, low and high divinylbenzene-crosslinked styrene copolymers, respectively.
• An example of a gelular resin is Amberlyst-121 (sulfonated, 4% divinylbenzene-crosslinked polystyrene resin) available commercially from the Rohm and Haas Company.
• An example of a macroreticular resin is Amberlyst-15 (sulfonated, 20% divinylbenzene-crosslinked polystyrene resin), also available commercially from the Rohm and Haas Company.
• an excess of the acidic medium is preferably employed to ensure complete conversion to the sulfonic acid.
• the acidic medium employed is a sulfonated styrene-divinylbenzene resin, and is used in an amount from about 15 times to about 20 times the number of moles of the alkali metal sulfonic acid salt. Higher amounts of the acidic medium can also be employed, but they are generally not required.
• the process of contacting the polymeric, strongly acidic resin with the alkali metal salt of the aromatic sulfonic acid is accomplished by allowing the solution to pass through a column packed with polymeric acidic resin.
• contacting is effected by pumping the solution from the bottom of the packed bed column and the solution of the product mixture is collected from the top of the bed.
• Suitable solvents for preparing a solution comprising the alkali metal salt of the aromatic sulfonic acid comprise water, C 1 -C 4 aliphatic alcohols, tetrahydrofuran, acetonitrile, C 7 -C 9 aromatic hydrocarbons, and mixtures thereof. Generally the presence of water facilitates the alkali metal ion-hydrogen ion exchange process.
• the aromatic sulfonic acid composition obtained from the alkali metal salt complex of formula (VII) is neutralized by contacting it with a quaternary compound represented by formula (VIII) as shown: X(R 4 ) 4 —Y (VIII), wherein “X” is selected from the group consisting of nitrogen and phosphorus; each R 4 is independently selected from substituted or unsubstituted aliphatic or aromatic radicals, or substituted or unsubstituted carbocyclic or heterocyclic radicals as previously described for the corresponding quaternary onium sulfonic acid salt of formula (I); and Y comprises a hydroxide, OCOR 5 , or OR 5 , wherein R 5 comprises a substituted or unsubstituted aliphatic, carbocyclic or aromatic, radical.
• suitable R 5 groups are selected from the group consisting of C 1 -C 8 linear and branched alkyl groups. In another embodiment, suitable R 5 groups are selected from the group consisting of C 6 -C 12 aryl groups. These quaternary ammonium and phosphonium compounds of formula (VIII) react with a sulfonic acid group to generate the corresponding quaternary ammonium or phosphonium sulfonate compounds in the reaction mixture.
• the quaternary compound of formula (VIII) is preferably selected from the group consisting of tetraethylphosphonium hydroxide, tetra-n-butylphosphonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-octylphosphonium hydroxide, and tetraphenylphosphonium hydroxide.
• the temperature of the reaction mixture is preferably maintained in the range from about 10° C. to about 50° C. In one embodiment, the temperature of the reaction mixture is maintained in the range from about 20° C. to about 30° C. In another embodiment the reaction is carried out at an autogenous temperature.
• the pH of the reaction mixture is preferably adjusted to about 4 to about 6, with a pH of about 5 to about 5.5 more preferred.
• Some surfactants are commercially available in the sulfonic acid forms.
• Dowfax 3B0 Surfactant is commercially available in the acid form from Dow Chemical Company.
• commercially available sulfonic acids can be directly reacted with the quaternary compounds with adjustment of the pH as described above to furnish the quaternary onium aromatic sulfonate compound.
• quaternary onium aromatic sulfonate compound is then extracted from the product mixture using a suitable solvent.
• suitable solvents include those that selectively dissolve the quaternary onium sulfonate compound.
• suitable solvents comprise halogenated aliphatic and aromatic compounds, aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and mixtures thereof.
• a suitable solvent for extraction is chloroform.
• substantially all of the solvent is removed.
• “substantially” means an amount which is greater than 90 weight percent (wt. %) removed, in other embodiments, greater than about 98 wt. % removed, in still other embodiments, greater than about 99 wt. % removed, based on the weight of solvent used.
• removal of substantially all the solvent means that no more condensate is obtained in the evaporation process.
• the method described above can be used for preparing benzene-1-methoxy-3-(n-pentadecyl)-4,6-ditetrabutylphosphoniumsulfonate (hereinafter sometime referred to as Formula (IX)).
• the method comprises mixing benzene-1-methoxy-3-(n-pentadecyl)-4,6-disulfonic acid with a tetra-n-butylphosphonium hydroxide quaternary compound.
• the required di-alkali metal salt of benzene-1-methoxy-3-(n-pentadecyl)-4,6-disulfonic acid can be prepared by employing a 3-step process starting from 3-pentadecylphenol. O-methylation of an alkali metal salt of 3-(n-pentadecyl)phenol with methyl iodide in a dipolar aprotic solvent, such as dimethylsulfoxide gives 3-(n-pentadecyl)anisole. This material is then sulfonated using concentrated sulfuric acid, oleum, or chlorosulfonic acid to form the disulfonic acid derivative.
• the product is a sulfonyl chloride derivative which upon hydrolysis forms the sulfonic acid.
• the disulfonic acid is isolated in a pure form as a di-alkali metal salt since this route helps in separating the organic impurities present in the sulfonation reaction mixture.
• Another example of the utility of the method described above is for making an alkylated diphenyloxide tetrabutylphosphoniumsulfonate compound having the formula (V).
• the starting material for making the compound shown in formula (V) is represented by the formula (X): wherein “T” is selected from hydrogen and sodium, and “a′” and R 2 are as described previously.
• the sodium salts of formula (X) wherein a′ is 1 is, for example commercially available from Dow Chemical Company under the trade name Dowfax® surfactants.
• the sulfonic acid forms of formula (X), wherein a′ is 1, and R 2 is a C 10 or a C 12 alkyl group is, for example commercially available from Dow Chemical Company.
• a polyorganosiloxane-functionalized aromatic sulfonate having the formula (VI) can be made by mixing in a suitable solvent, a hydroxyalkyl-terminated polydimethylsiloxane having the formula (XI), (XI), wherein “n′′” has a value of about 7; a quaternary sulfonate salt of an aromatic sulfocarboxylic acid having the formula (XII): (XII), wherein R 1 and “X” are as previously described, and a catalyst.
• the resulting mixture is then preferably heated with stirring for a suitable duration to effect an esterification reaction and form the desired product.
• the reaction mixture is then preferably heated to a temperature of about 50° C.
• the duration of heating is preferably from about 8 hours to about 30 hours, with about 12 hours to about 26 hours more preferred, and from about 18 hours to about 24 hours even more preferred.
• the catalyst composition comprises at least one carbodiimide compound of the formula (XIII): (XIII), wherein R 6 is independently selected from monovalent alkyl and aryl, substituted and unsubstituted radicals; 1-hydroxybenzotriazole, and at least one nitrogen base selected from the group consisting of tertiary amines of the formula (R 7 ) 3 N, where R 7 is independently selected from C 1 -C 8 linear and branched alkyl groups; and heterocyclic nitrogen bases.
• the heterocyclic nitrogen base that can be used include, but are not limited to substituted and unsubstituted pyridines, imidazoles, and pyrrolidines.
• the carbodiimide compound is at least one selected from the group consisting of 1,3-dicyclohexylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, and 1,3-diisopropylcarbodiimide.
• the solvent for the esterification reaction comprises C 1 -C 4 nitriles, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluenes.
• Acetonitrile is a preferred solvent for this reaction since it can be easily removed by evaporation and facilitates product isolation.
• the quaternary sulfonate salt of a sulfocarboxylic acid used is represented by formula (XII) in which R 1 is an n-butyl group, and “X” is selected from the group consisting of phosphorus and nitrogen.
• the preparation of the bis (tetrabutylphosphonium) polyorganosiloxane-functionalized aromatic sulfonate formula (VI) as previously shown preferably comprises the use of a solvent selected from the group consisting of C 1 -C 4 nitrites, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluenes.
• a solvent selected from the group consisting of C 1 -C 4 nitrites, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluenes.
• Acetonitrile is a preferred solvent for this reaction.
• Product formation is accomplished by heating the reaction mixture, whereby the temperature is maintained from about 50° C. to the refluxing temperature of the reaction mixture, and more preferably, from about 50° C. to about 85° C.
• the quaternary aromatic onium sulfonate compounds may have surface migratory aptitude that can aid in dissipation of localized static charge accumulated on a polymer surface. These compounds possess a polar, hydrophilic onium sulfonate group, and a non-polar, hydrophobic moiety. While not wanting to be bound by theory, it is believed that the polar group attracts ambient moisture to form a layer of water molecules on the polymer surface. These water molecules in turn are hydrogen bonded to each other. Dissipation of the localized surface charge occurs through this hydrogen-bonded layer of water molecules, thus leading to antistatic activity.
• the quaternary aromatic onium sulfonate compounds can be incorporated into polymers, particularly thermoplastic polymers, together with other additives during the molding process to afford antistatic polymer molding compositions without adversely affecting the transparency properties.
• polymers particularly thermoplastic polymers
• Such polymer molding compositions are commercially valuable for preparing antistatic articles.
• the articles that can be prepared using the above polymer molding compositions are those comprising forward lighting assemblies, automotive headlamp lenses, fog lamp lenses, ophthalmic devices, printer devices, and display panel devices for appliances.
• thermoplastic molding compositions include those comprising aromatic polycarbonate, polyestercarbonate, polyphenylene sulfide, polyetherimide, polyester, polyphenylene ether, polyphenylene ether/styrene polymer blends, polyamide, polyketone, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polyolefin, blends thereof, and blends thereof with other materials, such as glass.
• a dry blending process includes preparing the polymer molding composition by mixing all of the components prior to subjecting the mixture to a molding process for fabricating the articles.
• the various components may include the polymer resin (powder, pellets, or the like), the quaternary aromatic onium sulfonate compounds and various additives such as, but not limited to, antioxidants, thermal stabilizers, ultraviolet stabilizers, processing agents, mold release agents, fillers, flame retardants, and the like.
• Another method for incorporating the quaternary aromatic onium sulfonate compounds into thermoplastic polymers comprises combining the ingredients, including at least one and/or antidust additives discussed above, with at least one polymer in a melt processing equipment.
• a solvent may be optionally added to aid in mixing with the rest of the feed mixture.
• the processing machine may have a devolatilization system to effectively remove volatiles such as the optional solvent during the processing step. Any melt processing equipment may be employed and those skilled in the art may choose appropriate equipment without undue experimentation depending upon such factors as the type of polymer to be processed.
• suitable melt processing equipment includes, but is not limited to, extruders, kneaders, roll-mills and similar equipment.
• the method of molding the above molding compositions may include at least one step of injection molding, sheet molding, thermoforming, and/or blow molding.
• molding may be accomplished using a molten feed stream, instead of a powder and/or pellet form of the thermoplastic polymer component.
• a molten feed stream instead of a powder and/or pellet form of the thermoplastic polymer component.
• This option is advantageous in a polymer production facility, wherein the final product exiting the polymerization process is in a neat molten state.
• the molten polymer is directly fed into a molding machine together with the quaternary aromatic onium sulfonate compound, together with other desired processing additives.
• the antistatic compositions described herein are useful for coating articles and for preparing fibers.
• the fibers can then be employed for manufacture of fabric and the like.
• T g Glass transition temperatures
• % T Perkin Elmer Model TGA-7 Thermogravimetric Analyzer.
• Percent transmission hereinafter referred to as “% T”
• YI yellowness index
• % Haze percent haze
• % ⁇ MVR percent change in melt viscosity ratio
• Tulsion T-42 MP (H + ) an acidic gel type ion exchange resin was purchased from Thermax Limited, India.
• the resin had moisture content of about 50-52% and an exchange capacity of about 1.8 milliequivalents of H + per unit volume of resin in the wet state (about 4.9 milliequivalents of H + per unit volume of resin in the dry state).
• the Dowfax® surfactants were procured from Dow Chemical Company.
• the mixture was extracted with ethyl acetate (3 ⁇ 100 ml) to remove unreacted 3-(n-pentadecyl)anisole as an ethyl acetate solution.
• the aqueous layer was neutralized with sodium bicarbonate and cooled to about 10° C. for about 3 hours.
• the precipitated sodium sulfate was filtered off, and the filtrate was diluted with n-butanol (500 ml).
• the n-butanol solution was concentrated on a rotary evaporator under reduced pressure.
• Methanol 500 ml was added to the residual material whereupon some more sodium sulfate precipitated out which was removed by filtration.
• the clarified disodium salt from above was dissolved in deionized water and the solution was passed through a column packed with Tulsion H + ion exchange resin (previously purified by washing with hot distilled water).
• the eluate from the column was collected and treated with tetra-n-butylphosphonium hydroxide (used as a 40% aqueous solution) until the pH of the reaction mixture was about 5.6.
• the reaction mixture was extracted with chloroform (500 ml); the chloroform solution was washed with deionized water, and dried over anhydrous sodium sulfate. Removal of the chloroform on a rotary evaporator, followed by drying under high vacuum using an oil pump afforded the product as a pale yellow viscous liquid. Proton NMR spectrum of the material showed that it was the desired product.
• alkylated diphenyloxide tetrabutylphosphoniumsulfonates of formula (XIV) with R 2 groups having varying alkyl chain lengths (A, B, C, and D) were prepared.
• alkylated diphenyloxide sulfonic acids that were commercially available were reacted with tetra-n-butylphosphonium hydroxide as follows.
• alkylated diphenyloxide sulfonate compounds (XIV-A), (XIV-B), (XIV-C), and (XIV-D) were prepared by starting from the corresponding C 6 , C 10 , C 12 , and C 16 alkylated diphenyl oxide sodium sulfonic acids, respectively.
• This example describes the synthesis of a bis(tetrabutylphosphonium) polyorganosiloxane-functionalized aromatic sulfonate compound (formula VI).
• the ether solution was separated, dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator.
• the residual oily product was distilled under reduced pressure. The fraction having a boiling range from about 65° C. to about 80° C. at about 0.06 mm Hg was collected. In this manner, 96 g of the desired bis(hydroxypropyl)-terminated poly (dimethylsiloxane) product was obtained. NMR analysis of the product indicated the material had a number average molecular weight (M n ) of about 770.
• an aromatic polycarbonate resin was melt-blended with the appropriate amount of the anti-static agent as indicated below.
• the aromatic polycarbonate resin used in the examples was a BPA homopolycarbonate resin having an intrinsic viscosity of about 0.46 deciliters per gram as measured in dichloromethane at 20° C.
• the molding mixture also contained 2.7 grams of silicone oil mold release agent per kilogram of molding mixture and 3.9 grams of stabilizers per kilogram of molding mixture, the addition of which are not believed to affect the antistatic properties.
• the molding mixture was molded in a 25 mm twin-screw extruder using an operating temperature of about 285° C.
• the resulting strands were quenched in water and cut into pellets, which were dried at about 120° C. for about 2 hours (h).
• the dried pellets were injection molded using a single screw injection-molding machine to produce 10 centimeters (cm) square plaques having a thickness of about 2.5 millimeters (mm).
• the maximum temperature for the injection-molding barrel was about 285° C.
• plaques required for carrying out the static decay tests were obtained from the larger plaques prepared above. Each plaque used for the static decay test measured about 78 mm ⁇ 58 mm ⁇ 2.5 mm. Prior to the test, the plaques were conditioned at a temperature of about 23° C. and a relative humidity of about 50% for about three days. The static decay tests were carried out on these plaques using a Static Honestmeter, Model S-5109 instrument manufactured by Shishido Electrostatic Ltd. The applied voltage was cut-off when the surface charge attained a fixed value of about 3 kilovolts. Subsequently, the decay of surface charge was followed with time with a detector.
• the static half decay time (indicated by “T 1/2 ”) represents the time at which the surface charge reached a value that was half the initial value.
• T 1/2 The above procedure was repeated for a control experiment where no antistatic additive was added.
• Table 2 refers to measurements made with plaques containing 25.6 mmol of the antistatic additive per kilogram of the polycarbonate.
• Table 3 refers to measurements made with plaques containing 1.5 weight percent of the antistatic additive relative to weight of the polycarbonate taken. “NA” in the tables means “not available”.

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